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WO1999012661A1 - Pretraitement avant peinture de structures de metal composite renfermant des portions d'aluminium - Google Patents

Pretraitement avant peinture de structures de metal composite renfermant des portions d'aluminium Download PDF

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Publication number
WO1999012661A1
WO1999012661A1 PCT/US1998/018001 US9818001W WO9912661A1 WO 1999012661 A1 WO1999012661 A1 WO 1999012661A1 US 9818001 W US9818001 W US 9818001W WO 9912661 A1 WO9912661 A1 WO 9912661A1
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WIPO (PCT)
Prior art keywords
moiety
ions
independently
unit
hydrogen
Prior art date
Application number
PCT/US1998/018001
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English (en)
Inventor
Peter Kuhm
Michael L. Sienkowski
Gerald J. Cormier
Matthias Hamacher
Jurgen Geke
Volkhard Enke
Jan-Willem Brouwer
Hubert Venschott
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22017075&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1999012661(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to US09/508,402 priority Critical patent/US6720032B1/en
Priority to PL98339252A priority patent/PL339252A1/xx
Priority to DE69840270T priority patent/DE69840270C5/de
Priority to JP2000510539A priority patent/JP2001515959A/ja
Priority to CA002303183A priority patent/CA2303183C/fr
Priority to AU93738/98A priority patent/AU756876B2/en
Priority to EP98946801A priority patent/EP1027170B1/fr
Priority to BR9812069-7A priority patent/BR9812069A/pt
Priority to KR1020007002586A priority patent/KR20010023902A/ko
Publication of WO1999012661A1 publication Critical patent/WO1999012661A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • aluminum is increasingly used in vehicle construction.
  • the expression "aluminum” refers not only to pure aluminum but also to aluminum alloys whose main
  • 5 component is aluminum.
  • Examples of commonly used alloying elements are silicon, magnesium, copper, manganese, chromium and nickel, the total proportion by weight of these alloying elements in the alloy normally not exceeding 10 %.
  • engine and gear parts, wheels, seat frames, etc. already contain large amounts of aluminum, the use of aluminum in bodywork construction is presently still restricted to parts such ⁇ o as hoods, rear trunk lids, inner door parts and various small parts as well as truck cabins, side walls of transporters or attachments to minivans.
  • Overall, worldwide less than 5 % of the metal surface of automobile bodies is made of aluminum. The increased use of aluminum in this sector is being intensively investigated by the aluminum and automobile industries.
  • This invention relates to a process for the corrosion-prevention pretreatment before painting of composite metal structures that contain aluminum and/or aluminum alloy portions in addition to steel and/or galvanized steel portions.
  • the process is particularly intended for use in automobile manufacturing.
  • car bodies or car body parts that contain structural portions of aluminum and/or its alloys in addition
  • ⁇ 5 mobile manufacturing in that a surface-covering zinc phosphate layer is deposited in a first step on the steel and/or galvanized steel surfaces, without coating the aluminum surfaces to any appreciable extent.
  • a second step comprises a treatment with a solution that does not excessively attack the previously formed zinc phosphate layer, and indeed preferably even enhances its corrosion-prevention action, and which simultaneously forms a surface layer on the aluminum surfaces.
  • a two-stage process is thus involved, whose first stage comprises a conventional zinc phosphating. It is a necessary condition, of course, that a zinc phosphating solution is used that does not form a layer on aluminum. Such zinc phosphating solutions are known in the prior art and are referred to by the way of example hereinafter.
  • a zinc phosphating solution is used that does not form a layer on aluminum.
  • Such zinc phosphating solutions are known in the prior art and are referred to by the way of example hereinafter.
  • solutions with constituents that are effective to form a protective layer on aluminum are used.
  • the nature and concentration of these solutions should be chosen so that on the one hand a layer is reliably formed on the aluminum surfaces, but on the other hand the crystalline zinc phosphation layers formed on the iron and/or zinc surfaces are not excessively damaged.
  • the aim of phosphating metals is to produce firmly adhering metal phosphate layers on the metal surface that per se already improve the corrosion resistance, and in conjunction with paints or other organic coatings contribute to a substantial improvement of the coating adhesion and resistance to creepage under corrosive stress.
  • Such phosphating processes have been known for a long time.
  • low zinc phosphating processes in which the phosphating solutions contain relatively small concentrations of zinc ions, for example 0.5 to 2 grams per liter, hereinafter usually abbreviated as "g/l", are particularly suitable.
  • a basic parameter in these low zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is normally above 8 and may reach values of up to 30.
  • phosphate layers with substantially improved corrosion- prevention and paint adhesion properties can be formed by the co-use of other polyvalent cations in the zinc phosphating baths.
  • low zinc processes with the addition of, e.g., 0.5 to 1.5 g/l of manganese ions and, e.g., 0.3 to 2.0 g/l of nickel ions are widely used as so-called "tri-cation" processes for preparing metal surfaces for painting, for example for cathodic electro-dipcoating of car bodies.
  • EP-A-459 541 describes phosphating solutions that are essentially free of nickel and that contain, in addition to zinc and phosphate, 0.2 to 4 g/l of manganese and 1 to 30 milligrams per liter, hereinafter usually abbreviated as "mg/l", of copper. From DE-A- 42 10 513 nickel-free phosphating solutions are known that contain, in addition to zinc and phosphate, 0.5 to 25 mg/l of copper ions as well as hydroxylamine as accelerator. These phosphating solutions optionally also contain 0.15 to 5 g/l of manganese.
  • German patent application DE 196 06 017.6 describes a phosphating solution, with a decreased heavy metal concentration, which contains 0.2 to 3 g/l of zinc ions, 1 to 150 mg/l of manganese ions, and 1 to 30 mg/l of copper ions.
  • This phosphating solution may optionally contain up to 50 mg/l of nickel ions and up to 100 mg/l of cobalt ions.
  • a further optional constituent is lithium ions in amounts of between 0.2 and 1.5 g/l.
  • DE 195 38 778 describes controlling the coating weight of phosphate layers by the use of hydroxylamine as accelerator.
  • the use of hydroxylamine and/or its compounds in order to influence the form of the phosphate crystals is known from a number of publications.
  • EP-A-315 059 discloses as a special effect of the use of hydroxylamine in phosphating baths the fact that on steel the phosphate crystals still occur in the desired columnar or nodular form, even if the zinc concentration in the phosphating bath exceeds the conventional range for low zinc processes. In this way it is possible to operate the phosphating baths with zinc concentrations up to 2 g/i and with weight ratios of phosphate to zinc of as low as 3.7.
  • the required hydroxylamine concentration is given as 0.5 to 50 g/l, preferably 1 to 10 g/l.
  • WO 93/03198 discloses the use of hydroxylamine as accelerator in tri-cation phosphating baths with zinc contents of between 0.5 and 2 g/l and nickel and manganese contents of in each case 0.2 to 1.5 g/l, specific weight ratios of zinc to the other divalent cations having to be maintained.
  • these baths contain 1 to 2.5 g/l of a "hydroxylamine accelerator", which according to the description denotes salts of hydroxylamine, preferably hydroxylamine ammonium sulfate.
  • a so-called passivating post-rinsing also termed post-passivation, is generally employed in this technology.
  • Treatment baths containing chromic acid are still widely used for this purpose. For reasons of work safety and environmental protection there is a tendency, however, to replace these chromium-containing passivating baths by chromium-free treatment baths.
  • Organo-reactive bath solutions containing complexing substituted poly- (vinylphenols) are known for this purpose. Examples of such compounds are described in DE-C-31 46 265.
  • Particularly effective polymers of this type contain amine substituents and may be obtained by a Mannich reaction between poly(vinylphenols) and aldehydes and organic amines. Such polymers are described for example in EP-B- 91 166, EP-B-319 016 and EP-B-319 017.
  • Polymers of this type are also used within the scope of the present invention, and accordingly the contents of the immediately aforementioned four documents, except to any extent that may be inconsistent with any explicit teaching herein, are hereby incorporated herein by reference.
  • the use of such polyvinyl phenol derivatives for the surface treatment of aluminum is known, for example, from the aforementioned EP-B-319 016.
  • WO 90/12902 discloses a chromium-free coating for aluminum, the aluminum surfaces being contacted with a treatment solution that has a pH in the range from about 2.5 to about 5.0 and contains, in addition to polyvinyl phenol derivatives, also phosphate ions as well as fluoro acids of the elements zirconium, titanium, hafnium and silicon.
  • US-A-5 129 967 discloses treatment baths for a no-rinse treatment (termed there as "dried in place conversion coating") of aluminum, containing:
  • EP-B-8 942 discloses treatment solutions, preferably for aluminum cans, containing:
  • DE-C-24 33 704 describes treatment baths to improve paint adhesion and permanent corrosion prevention on, inter alia, aluminum, which may contain 0.1 to 5 g/l of poly- acrylic acid or its salts or esters as well as 0.1 to 3.5 g/l of ammonium fluorozirconate, calculated as Zr0 2 .
  • the pH of these baths may vary over a wide range. The best results are generally obtained when the pH is between 6 and 8.
  • US-A-4 992 116 describes treatment baths for the conversion treatment of aluminum with pH values between about 2.5 and 5, which contain at least three components: (a) phosphate ions in the concentration range between 1.1x10 "5 to 5.3x10 "3 moie/l, corresponding to 1 to 500 mg/l, (b) 1.1x10 "5 to 1.3x10 "3 mole/liter, hereinafter usually abbreviated as "mole/I", of a fluoro acid of an element of the group Zr, Ti, Hf and Si (corresponding to 1.6 to 380 mg/l of each element) and (c) 0.26 to 20 g/l of a polyphenol compound obtainable by reacting poly(vinylphenol) with aldehydes and organic amines.
  • a molar ratio of fluoro acid to phosphate of about 2.5:1 to about 1:10 should be maintained.
  • DE-A-27 15 292 discloses treatment baths for the chromium-free pretreatment of aluminum cans, which contain at least 10 parts per million by weight, hereinafter usually abbreviated as "ppm", of titanium and/or zirconium, between 10 and 1000 ppm of phosphate, and a sufficient amount of fluoride, but at least 13 ppm, to form complex fluorides of the titanium and/or zirconium present, and have pH values of between 1.5 and 4.
  • WO 92/07973 discloses a chromium-free treatment process for aluminum, which uses as essential components in acid aqueous solution 0.01 to about 18 wt. % of H 2 ZrF 6 and 0.01 to about 10 wt.
  • % of a 3-(N-C lJ( alkyl-N-2-hydroxyethyl-aminomethyl)-4-hydroxy- styrene polymer optionally include 0.05 - 10 wt. % of dispersed Si0 2 , 0.06 to 0.6 wt. % of a solubilizing agent for the polymer, as well as a surfactant.
  • the afore- mentioned polymer is included among the "reaction products of poly(vinylphenol) with aldehydes and organic hydroxyi group-containing amines" described below and that can be used within the scope of the present invention.
  • the fluoride ions mask the aluminum ions by complex formation and/or precipitate these ions as hexa-fiuoroaluminates of sodium and/or potassium if the solubility products of the corresponding salts are exceeded. Furthermore free fluoride ions usually lead to an increased etching attack on the aluminum surfaces, with the result that a more or less closed and sealed zinc phosphate layer can form on the latter.
  • the joint phosphating of aluminum structural portions with those of steel and/or galvanized steel thus has the technical disadvantage that the phosphating baths have to be very accurately monitored as regards their fluoride content. This increases the control and monitoring work involved and may require stocking and metering fluoride- containing solutions as separate replenishment solutions. Also, the precipitated hexafluoroaluminate salts increase the amount of phosphating sludge and raise the cost of its removal and disposal.
  • This object is achieved by a process for the chemical pretreatment, before an organic coating, of composite metal structures that contain aluminum or aluminum alloy portions together with steel, galvanized steel and/or alloy-galvanized steel portions, characterized by: (I) treating in a first step the composite metal structure with a zinc phosphating solution that forms on steel and on galvanized and/or alloy-galvanized steel a surface-covering crystalline zinc phosphate layer having a coating weight in the range from 0.5 to 5 g/m 2 , but without forming a zinc phosphate layer on the aluminum portions; and subsequently, with or without intermediate rinsing with water,
  • step (II) contacting in a second step the composite metal structure with a treatment solution that does not dissolve more than, with increasing preference in the order given, 60, 50, 40, 30, 20, 15, 10, 8, or 6 % of the crystalline zinc phosphate layer formed on steel, galvanized and/or alloy-galvanized steel in step (I), but does produce a conversion layer on the aluminum portions.
  • the concentration of free fluoride ions for example, measured in g/l should satisfy the condition that, at a specific temperature T (in °C), it lies above a value of 8/T. Since however within the scope of the present invention no zinc phosphate layer should be formed on aluminum in the phosphating step (I), in contrast to the teaching of EP-B-452 638, at a specific temperature T (in °C) the concentration of free fluoride ions (in g/i) in the phosphating solution must be below 8 T.
  • a zinc phosphating solution which has a pH in the range from about 2.5 to about 3.6 and a temperature in the range from about 20 to about 65 °C, and which does not contain more free fluoride in g/l than is specified by the expression 8/T, "T denoting the bath temperature in °C, is preferably used.
  • this zinc phosphating solution preferably also comprises: 0.3 to 3 g/l of Zn(ll), 5 to 40 g/l of phosphate ions, and at least one of the following accelerators: 0.3 to 4, or more preferably 1 to 4, g/l of chlorate ions,
  • step (I) additionally contains one or more of the following cation concentrations:
  • the zinc concentration is more preferably in the range between about 0.8 and about 1.6 g/l.
  • Such zinc concentrations are adjusted in a working phosphating bath if during the phosphating of galvanized surfaces additional zinc passes into the phosphating bath through its etching action.
  • the man- ganese content may be in the range from about 0.001 to 0.2 g/l. Otherwise manganese contents of about 0.5 to about 1.5 g/l are conventional.
  • lithium ions in amounts of about 0.2 to about 1.5 g l improve the corrosion prevention that can be achieved with zinc phosphating baths.
  • Lithium concentrations in the range from 0.2 to about 1.5 g/i and in particular from about 0.4 to about 1 g/l also have a beneficial effect on the resultant corrosion prevention with the phosphating process according to the invention and subsequent post- treatment.
  • the phosphating baths as a rule also contain sodium, potassium and/or ammonium ions to adjust the free acid.
  • free acid is well known to those skilled in the art in the phosphating field. The method chosen to determine free acid as well as the total acid in this step is specified in the examples. Free acid and total acid represent an important control parameter for phosphating baths, since they have a large influence on the coating weight.
  • accelerators For the phosphating of zinc surfaces it would not be absolutely necessary for the phosphating baths to contain so-called accelerators.
  • phosphating steel surfaces it is, however, necessary for the phosphating solution to contain one or more accelerators.
  • Such accelerators are conventionally used in the prior art as components of zinc phosphating baths.
  • the term accelerators refers to substances that chemically react with the hydrogen produced on the metal surface by the etching action of the acid in such a way that they are themselves reduced.
  • Oxidizing accelerators furthermore have the effect of oxidizing iron(ll) ions released by the etching action on steel surfaces to the trivalent oxidation state, so that they can precipitate out as iron (III) phosphate.
  • step (II) solutions according to the prior art that produce a conversion layer on aluminum may be used. These solutions must not, however, excessively dissolve the crystalline zinc phosphate layer formed in step (I).
  • the pH of these solutions should therefore lie in the range from 2.5 to 10, preferably from 3.3 to 10.
  • solutions are chosen containing components that additionally passivate the crystalline zinc phosphate layers. Such solutions are mentioned hereinafter by way of example.
  • the metal structures are generally brought into contact with the treatment solutions by spraying or by dipping.
  • the temperature of the treatment solution for step (II) is preferably chosen in the range from 20 to 70 °C.
  • a treatment solution may be used that has a pH in the range from about 5 to about 5.5 and that contains overall about 0.3 to about 1.5 g/l of hexafluorotitanate and/or hexafluorozirconate ions. It may be advantageous for the corrosion protection of the crystalline zinc phosphate layer produced in step (I) if this treatment solution additionally contains about 0.01 to 0.1 g/l of copper ions for step (II).
  • a treatment solution may be used in step (II) that has a pH in the range from 3.5 to 5.8 and that contains 10 to 500 mg/l of organic polymers chosen from poly-4-vinylphenol compounds of the immediately following general formula (I):
  • n is an integer between 5 and 100
  • each of X and Y independently of each other denotes hydrogen or a CRR 1 OH moiety in which each of R and R independently is hydrogen or an aliphatic or aromatic moiety with 1 to 12 carbon atoms.
  • step (II) in particular those treatment solutions are preferred that contain poryvinylphenol derivatives according to the teaching of EP-B-319 016. This document also discloses the preparation of such polyvinylphenol derivatives. Accordingly, in step (II) a treatment solution is preferably used that has a pH in the range from 3.3 to 5.8 and contains 10 to 5000 mg/l of organic polymers selected from homopolymer or copolymer compounds containing amino groups, comprising at least one polymer selected from the group consisting of materials ( ⁇ ) and ( ⁇ ), wherein:
  • each of R 2 through R 4 is selected, independently of each other and independently from one molecule of the component to another and from one to another unit of any polymer molecule conforming to this formula when there is more than one such unit in a single polymer molecule, from the group consisting of a hydrogen moiety, an alkyl moiety with from 1 to 5 carbon atoms, and an aryl moiety with from 6 to 18 carbon atoms; each of Y 1 through Y 4 is selected, independently of each other and independently from one molecule of the component to another and from one to another unit of any polymer molecule conforming to this formula when there is more than one such unit in a single polymer molecule, except as noted further below, from the group consisting of: a hydrogen moiety; a -CH 2 CI moiety; an alkyl moiety with from 1 to 18 carbon atoms; an aryl moiety with from 6 to 18 carbon atoms; a moiety conforming to the general formula -CR 12 R 3 OR 14 , where each of R 12
  • each of R 5 through R ⁇ is selected, independently of each other and independently from one molecule of the component to another and from one to another unit of any polymer molecule conforming to this formula when there is more than one such unit in a single polymer molecule, from the group consisting of a hydrogen moiety, an alkyl moiety, an aryl moiety, a hydroxyalkyl moiety, an aminoalkyl moiety, a mercaptoalkyl moiety, and a phosphoalkyl moiety and R 9 is selected from the group consisting of a hydrogen moiety, an alkyl moiety, an aryl moiety, a hydroxy or polyhydroxy alkyl moiety, an amino or polyamino alkyl moiety, a mercapto or polymercapto alkyl moiety, a phospho or polyphospho alkyl moiety, an -O " moiety, and an -OH moiety, at least one of Y 1 through Y 4 in at least one unit of each selected polymer molecule being
  • each of R 10 and R 11 is selected, independently of each other and independently from one molecule of the component to another and from one to another unit of any polymer molecule conforming to this formula when there is more than one such unit in a single polymer molecule, from the group consisting of a hydrogen moiety, an alkyl moiety with from 1 to 5 carbon atoms, and an aryl moiety with from 6 to 18 carbon atoms; each of Y 4 through Y 6 is selected, independently of each other and independently from one molecule of the component to another and from one to another unit of any polymer molecule conforming to this formula when there is more than one such unit in a single polymer molecule, except as noted further below, from the group consisting of: a hydrogen moiety; a -CH 2 CI moiety; an alkyl moiety with from 1 to 18 carbon atoms; an aryl moiety with from 6 to 18 carbon atoms; a moiety conforming to the general formula -CR 12 R 13 OR 14 , where each of
  • materials ( ⁇ ) and/or ( ⁇ ) predominantly molecules which consist entirely, except for relatively short end groups, of units conforming to one of the general formulas (I) and (II) as described above.
  • materials are generally prepared by reacting homopolymers of ⁇ -vinyl phenol, for material ( ⁇ ), or phenol-aldehyde condensation products, for material ( ⁇ ), with formaldehyde and secondary amines to graft moieties Z on some of the activated benzene rings in the materials thus reacted.
  • material ( ⁇ ) is material in which the polymer chains are at least predominantly copoiymers of simple or substituted 4-vinyl phenol with another vinyl monomer such as acrylonitrile, metha- crylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, vinyl methyl ketone, iso- propenyi methyl ketone, acrylic acid, methacrylic acid, acrylamide, methacryiamide, n- amyl methacrylate, styrene, m-bromostyrene, rj-bromostyrene, pyridine, diallyldimethyl- ammonium salts, 1,3-butadiene, ⁇ -butyl acrylate, t-butylamino-ethyl methacrylate, n- butyl methacrylate, t-butyl methacrylate, n-butyl vinyl ether, t-butyl vinyl ether
  • each of R 2 through R 6 , R 10 , R 11 , W ⁇ and W 2 independently for each and from one unit to another in the same or a different molecule, preferably is a hydrogen moiety
  • each of Y 1 through Y 6 independently for each and from one unit to another in the same or a different molecule, preferably is a hydrogen moiety or a moiety Z
  • each polymer molecule contains a number of units corresponding to one of gen- eral formulas (II) and (III) as defined above that is at least, with increasing preference in the order given, 2, 3, 4, 5, 6, 7, or 8 and independently preferably is not more-tharrlQG, 75, 50, 40, 30, or20r in the total of materials ( ⁇ ) and ( ⁇ ) in a composition used in step (II) according to the invention, the number of moie
  • Poly(5-vinyl-2-hydroxy-N-benzyl)-N-methylglucamine is a specific polymer of the most preferred type, which, in the acidic pH range which is to be established, is present at least in part as an ammonium salt.
  • Solutions may be used that do not contain any further active constituents, apart from the polyvinyl phenol derivative and an acid for adjusting the pH, preferably phos- phoric acid. Additions of further active constituents, in particular hexafluorotitanate or hexafiuorozirconate ions, may however improve the layer formation on aluminum.
  • a solution may be used whose pH lies preferably in the range from about 3.3 to about 5.8 and which contains as organic polymer about 100 to about 5000 mg/l of an organic polymer in the form of a methylethanolamine derivative or N-methylglucamine derivative of polyvinyl phenol and in addition 10 to 2000 mg/l of phosphate ions, 10 to 2500 mg/l of hexafluorotitanate or hexafiuorozirconate ions, and 10 to 1000 mg/l of manganese ions.
  • step (II) there may be used in step (II) solutions or dispersions of organic polymers se- lected from homopolymers and/or copolymers of acrylic acid and methacrylic acid as well as their esters.
  • these solutions or dispersions have pH values in the range from about 3.3 to about 4.8 and contain about 250 to about 1500 mg/i of organic polymers.
  • these polymer solutions or dispersions may additionally contain hexafluorotitanates, hexafluorozirconates and/or hexafluorosilicates.
  • a process sequence according to the invention was tested on sample metal sheets of cold roiled steel (hereinafter usually abbreviated as “CRS”), electrolytically galvanized steel (hereinafter usually abbreviated as “ZE”), electrolytically zinc-iron-coated steel (hereinafter usually abbreviated as “ZFE”) and on aluminum 6111.
  • CRS cold roiled steel
  • ZE electrolytically galvanized steel
  • ZFE electrolytically zinc-iron-coated steel
  • the corrosion resistance tests were carried out according to the GM9540P-B process cycle of General Motors, which consists of the following steps:
  • Table 1 shows the compositions of the three post-rinse solutions, and Tables 2 and 3 show the zinc phosphate coating etch amounts and the average paint creepages at the scribe (full scribe width) respectively.
  • Table 1 POST-RINSE COMPOSITIONS

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Dans un procédé de prétraitement chimique, effectué avant de peindre des structures de métal composite renfermant de l'aluminium ou des portions en alliage d'aluminium et d'acier, d'acier galvanisé, et/ou en alliage-acier galvanisé, on traite tout d'abord ladite structure de métal au moyen d'une solution de phosphate de zinc, qui forme une couche de phosphate de zinc cristalline sur la surface de l'acier, de l'acier galvanisé, ou des portions en alliage-acier galvanisé, sans pour autant former une couche de phosphate de zinc sur les portions d'aluminium. Au cours d'une seconde étape, on met ladite structure de métal en contact avec une solution de traitement permettant de ne pas dissoudre excessivement la couche de phosphate de zinc cristalline formée sur l'acier, l'acier galvanisé, et/ou les portions en alliage-acier galvanisé, cette solution étant destinée à former, sur lesdites portions d'aluminium, une couche métallique obtenue par conversion chimique.
PCT/US1998/018001 1997-09-10 1998-09-04 Pretraitement avant peinture de structures de metal composite renfermant des portions d'aluminium WO1999012661A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US09/508,402 US6720032B1 (en) 1997-09-10 1998-09-04 Pretreatment before painting of composite metal structures containing aluminum portions
PL98339252A PL339252A1 (en) 1997-09-10 1998-09-04 Pre-treatment of metallic composite structures incorporating aluminium parts before painting them
DE69840270T DE69840270C5 (de) 1997-09-10 1998-09-04 Vorbehandlung zum färben von kompositmaterialien, die aluminiumteile enthalten
JP2000510539A JP2001515959A (ja) 1997-09-10 1998-09-04 アルミニウム部分を有する複合金属構造体の塗装の前処理
CA002303183A CA2303183C (fr) 1997-09-10 1998-09-04 Pretraitement avant peinture de structures de metal composite renfermant des portions d'aluminium
AU93738/98A AU756876B2 (en) 1997-09-10 1998-09-04 Pretreatment before painting of composite metal structures containing aluminum portions
EP98946801A EP1027170B1 (fr) 1997-09-10 1998-09-04 Pretraitement avant peinture de structures de metal composite renfermant des portions d'aluminium
BR9812069-7A BR9812069A (pt) 1997-09-10 1998-09-04 Processo para o pré-tratamento quìmico, antes de um revestimento orgânico, de uma estrutura metálica compósita.
KR1020007002586A KR20010023902A (ko) 1997-09-10 1998-09-04 알루미늄 부분을 포함하는 복합 금속 구조물의 도장전전처리

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5848197P 1997-09-10 1997-09-10
US60/058,481 1997-09-10

Publications (1)

Publication Number Publication Date
WO1999012661A1 true WO1999012661A1 (fr) 1999-03-18

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PCT/US1998/018001 WO1999012661A1 (fr) 1997-09-10 1998-09-04 Pretraitement avant peinture de structures de metal composite renfermant des portions d'aluminium

Country Status (13)

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EP (1) EP1027170B1 (fr)
JP (1) JP2001515959A (fr)
KR (1) KR20010023902A (fr)
CN (1) CN1157263C (fr)
AU (1) AU756876B2 (fr)
BR (1) BR9812069A (fr)
CA (1) CA2303183C (fr)
DE (1) DE69840270C5 (fr)
ES (1) ES2316169T3 (fr)
PL (1) PL339252A1 (fr)
TR (1) TR200000657T2 (fr)
WO (1) WO1999012661A1 (fr)
ZA (1) ZA988202B (fr)

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WO2002066702A1 (fr) 2001-02-16 2002-08-29 Henkel Kommanditgesellschaft Auf Atkien Procede de traitement d'articles polymetalliques
JP2004507615A (ja) * 2000-07-27 2004-03-11 ロード　コーポレーション 二液型水性金属保護処理
WO2004101850A1 (fr) * 2003-05-19 2004-11-25 Henkel Kommanditgesellschaft Auf Aktien Pretraitement de surfaces metalliques avant une mise en peinture
EP1550740A1 (fr) 2003-12-29 2005-07-06 Henkel Kommanditgesellschaft auf Aktien Procédé de couche de conversion à plusieurs étapes
WO2012000894A1 (fr) 2010-06-30 2012-01-05 Henkel Ag & Co. Kgaa Procédé de phosphatation sélective d'une construction métallique composite
WO2013033372A1 (fr) * 2011-09-02 2013-03-07 Ppg Industries Ohio, Inc. Procédé de phosphatation au zinc en deux étapes
US8399061B2 (en) 2006-11-13 2013-03-19 Basf Coatings Gmbh Anti-corrosion agent forming a coating film with good adhesion and method for nongalvanic application thereof
US8475883B2 (en) 2005-05-23 2013-07-02 Basf Coatings Gmbh Corrosion-protection agent forming a layer of paint and method for current-free application thereof
US8801871B2 (en) 2006-11-08 2014-08-12 Henkel Ag & Co. Kgaa Zr-/Ti-containing phosphating solution for passivation of metal composite surfaces
US9259730B2 (en) 2011-10-10 2016-02-16 Akman Serhan Tube to produce platelet rich fibrin
US10137476B2 (en) 2009-02-05 2018-11-27 Basf Coatings Gmbh Coating agent for corrosion-resistant coatings
USD837294S1 (en) 2016-12-23 2019-01-01 Comau S.P.A. Educational robot
WO2019158508A1 (fr) 2018-02-19 2019-08-22 Chemetall Gmbh Procédé de phosphatation sélective d'une construction métallique composite
WO2020074527A1 (fr) * 2018-10-08 2020-04-16 Chemetall Gmbh Procédé de phosphatation sans nickel de surfaces métalliques et composition destinée à être utilisée dans un tel procédé
WO2020074529A1 (fr) * 2018-10-08 2020-04-16 Chemetall Gmbh Procédé de phosphatation sans nickel de surfaces métalliques et composition destinée à être utilisée dans un tel procédé
EP3643759A1 (fr) * 2018-10-26 2020-04-29 Henkel AG & Co. KGaA Acier à feuillard revêtu de polycarboxylate et son utilisation pour l'emboutissage
US10762801B2 (en) 2016-12-23 2020-09-01 Comau S.P.A. Functional device, in particular a robot, for educational use with modules that can be combined together

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JP4795646B2 (ja) * 2003-10-01 2011-10-19 日新製鋼株式会社 耐食性，塗装性，接着性に優れた亜鉛系めっき鋼板
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WO2014035691A1 (fr) 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Compositions de prétraitement du zirconium qui contiennent du molybdène, procédés associés permettant de traiter des substrats métalliques et substrats métalliques recouverts associés
RU2609585C2 (ru) 2012-08-29 2017-02-02 Ппг Индастриз Огайо, Инк. Циркониевые композиции для предварительной обработки, содержащие литий, соответствующие способы обработки металлических субстратов и соответствующие металлические субстраты с покрытиями
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
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CN113930096A (zh) * 2020-06-29 2022-01-14 Ａｇｃ株式会社 复合材料、其制造方法和用途
JP7169326B2 (ja) * 2020-09-03 2022-11-10 株式会社神戸製鋼所 電動車両用バッテリーケースおよび製造方法
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CN115261841A (zh) * 2022-06-30 2022-11-01 东风商用车有限公司 一种钢铝混合基材的处理工艺

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004507615A (ja) * 2000-07-27 2004-03-11 ロード　コーポレーション 二液型水性金属保護処理
WO2002066702A1 (fr) 2001-02-16 2002-08-29 Henkel Kommanditgesellschaft Auf Atkien Procede de traitement d'articles polymetalliques
US6733896B2 (en) 2001-02-16 2004-05-11 Henkel Corporation Process for treating steel-, zinc- and aluminum-based metals using a two-step coating system
EP1368507A4 (fr) * 2001-02-16 2009-11-25 Henkel Ag & Co Kgaa Procede de traitement d'articles polymetalliques
WO2004101850A1 (fr) * 2003-05-19 2004-11-25 Henkel Kommanditgesellschaft Auf Aktien Pretraitement de surfaces metalliques avant une mise en peinture
EP1550740A1 (fr) 2003-12-29 2005-07-06 Henkel Kommanditgesellschaft auf Aktien Procédé de couche de conversion à plusieurs étapes
US8475883B2 (en) 2005-05-23 2013-07-02 Basf Coatings Gmbh Corrosion-protection agent forming a layer of paint and method for current-free application thereof
US8801871B2 (en) 2006-11-08 2014-08-12 Henkel Ag & Co. Kgaa Zr-/Ti-containing phosphating solution for passivation of metal composite surfaces
US8956468B2 (en) 2006-11-08 2015-02-17 Henkel Ag & Co. Kgaa Zr-/Ti-containing phosphating solution for passivation of metal composite surfaces
US8399061B2 (en) 2006-11-13 2013-03-19 Basf Coatings Gmbh Anti-corrosion agent forming a coating film with good adhesion and method for nongalvanic application thereof
US10137476B2 (en) 2009-02-05 2018-11-27 Basf Coatings Gmbh Coating agent for corrosion-resistant coatings
WO2012000894A1 (fr) 2010-06-30 2012-01-05 Henkel Ag & Co. Kgaa Procédé de phosphatation sélective d'une construction métallique composite
US9550208B2 (en) 2010-06-30 2017-01-24 Henkel Ag & Co. Kgaa Method for selectively phosphating a composite metal construction
DE102010030697A1 (de) 2010-06-30 2012-01-05 Henkel Ag & Co. Kgaa Verfahren zur selektiven Phosphatierung einer Verbundmetallkonstruktion
WO2013033372A1 (fr) * 2011-09-02 2013-03-07 Ppg Industries Ohio, Inc. Procédé de phosphatation au zinc en deux étapes
US9259730B2 (en) 2011-10-10 2016-02-16 Akman Serhan Tube to produce platelet rich fibrin
USD837294S1 (en) 2016-12-23 2019-01-01 Comau S.P.A. Educational robot
US10762801B2 (en) 2016-12-23 2020-09-01 Comau S.P.A. Functional device, in particular a robot, for educational use with modules that can be combined together
WO2019158508A1 (fr) 2018-02-19 2019-08-22 Chemetall Gmbh Procédé de phosphatation sélective d'une construction métallique composite
WO2020074527A1 (fr) * 2018-10-08 2020-04-16 Chemetall Gmbh Procédé de phosphatation sans nickel de surfaces métalliques et composition destinée à être utilisée dans un tel procédé
WO2020074529A1 (fr) * 2018-10-08 2020-04-16 Chemetall Gmbh Procédé de phosphatation sans nickel de surfaces métalliques et composition destinée à être utilisée dans un tel procédé
EP3643759A1 (fr) * 2018-10-26 2020-04-29 Henkel AG & Co. KGaA Acier à feuillard revêtu de polycarboxylate et son utilisation pour l'emboutissage
WO2020083645A1 (fr) * 2018-10-26 2020-04-30 Henkel Ag & Co. Kgaa Feuillard d'acier revêtu de polycarboxylate et son utilisation pour un emboutissage profond

Also Published As

Publication number Publication date
EP1027170A4 (fr) 2006-08-16
ES2316169T3 (es) 2009-04-01
DE69840270D1 (de) 2009-01-08
PL339252A1 (en) 2000-12-04
ZA988202B (en) 1999-03-09
DE69840270C5 (de) 2012-08-02
BR9812069A (pt) 2000-09-26
AU756876B2 (en) 2003-01-23
EP1027170B1 (fr) 2008-11-26
CA2303183A1 (fr) 1999-03-18
CN1157263C (zh) 2004-07-14
JP2001515959A (ja) 2001-09-25
CN1274305A (zh) 2000-11-22
EP1027170A1 (fr) 2000-08-16
TR200000657T2 (tr) 2000-07-21
AU9373898A (en) 1999-03-29
CA2303183C (fr) 2009-09-01
KR20010023902A (ko) 2001-03-26

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